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Lecture 14. Chemistry of Groups I, II, III and IV: (Cyclic Polyether)
Lecture 14. Chemistry of Groups I, II, III and IV: (Cyclic Polyether)
Chemistry of
Groups I, II, III and IV
ethereal
oxygens
(cyclic polyether)
H+
[H(OH2)2]+.4H2O
The hydride anion, HThe electron affinity of H is high enough that it can form a
negative hydride anion, H-, where it achieves the He
electron configuration. However, H- is a very strong Lewis
base. Thus, H- displaces OH- from water to give H2 and
OH-, showing that it is a stronger base than OH-:
H- (aq) + H2O =
Hydride as a ligand:
H
H
Al
H
Al
H
H
H
bridging hydride
[Al2H6]
[Fe(CO)4H2]
Hydrogen bonding:
One of the most important properties of the proton is its ability to
form H-bonds when attached to more electronegative donor atoms
such as F, O, or N. An H-bond is judged to be present when the
separation between the two atoms forming the H-bond is less than
the sum of the van der Waals radii. For H-bonds typical X-H-X
distances between
X atoms are:
O- -H- -O 2.76
F- - H- -F 2.55
N- -H- -N 3.00
Na+
K+
Rb+
Cs+
Li+
Na+ K+
Rb+
0.76 1.02 1.38 1.52
4-6 6-7 6-8 8-9
Cs+
1.67
8-9
Figure 3. A four
coordinate complex
of Li+ is seen (left) with
four THF (tetrahydrofuran)
molecules attached to
the Li+.
18-crown-6
15-crown-5
O
N O
O
O
O N
O
cryptand-222
O
N
O
O
O
12-crown-4
O
N
cryptand-221
O
O
24-crown-8
N O
O
O
O N
O
cryptand-211 cryptand-322
Cryptands:
Cryptand-2,2,2
O
O
O
O
O
K+ cryptand-2,2,2 complex:
K+
cryptand
Na+
Ca2+
La3+
Th4+
1.00
10.65
1.03
15.36
0.94
23.2
H2O OH2
O
O
O O
O
O
Ca
O
N
N
[Ca(EDTA)(H 2O)2]2-
EDTA
18-crown-6 15-crown-5
log K1(K+):
log K1(Ba2+):
2.05 0.75
3.89 1.71
cryptand-222
5.5
9.6
Al(III)
0.58
9.0
16.4
Ga(III)
0.62
11.410.6
20.4
In(III)
Tl(III)
0.80
0.89
13.4
25.0
35.3
increasing electronegativity
Al3+
Ga3+
In3+
Tl3+
log K1 (F-):
6.42
4.47
3.74
2.6
log K1 (Cl-):
-1.0
0.01
2.32
6.72
HARD
SOFT
position of
lone pair
Boron
Boron is very different in its chemistry from the other
members of the group. While they all have preferred
coordination numbers of 6, with occasional higher
coordination numbers of 7 or 8, boron always has a
coordination number of four or less. Thus, B(III) in aqueous
solution exists as B(OH)3(aq) at lower pH, and is too acidic
to ever be protonated to yield a B3+ (aq) ion. At higher pH
(9.1) a water coordinated to B(OH)3 (aq) ionizes to yield the
borate anion:
borate anion
Figure 9. B2H6,
showing the
bridging H-atoms,
which donate
electron density
to the adjacent
B atom.
Pb
Sn
Cl
Cl
Cl
[SnCl3]-
[Pb(C6H5)3]-
phenyl
group